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Influence of the Ligand Alkyl Chain Length on the Solubility, Aqueous Speciation, and Kinetics of Substitution Reactions of Water-Soluble M3S4 (M = Mo, W) Clusters Bearing Hydroxyalkyl Diphosphines
dc.contributor.author | Beltrán Álvarez, Tomás Francisco | |
dc.contributor.author | Llusar, Rosa | |
dc.contributor.author | Sokolov, Maxim | |
dc.contributor.author | García Basallote, Manuel | |
dc.contributor.author | Fernández-Trujillo, M. Jesús | |
dc.contributor.author | Pino Chamorro, Jose Angel | |
dc.date.accessioned | 2014-04-07T14:53:31Z | |
dc.date.available | 2014-04-07T14:53:31Z | |
dc.date.issued | 2013 | |
dc.identifier.citation | Inorg. Chem., 2013, 52 (15), pp 8713–8722 | ca_CA |
dc.identifier.issn | 0020-1669 | |
dc.identifier.issn | 1520-510X | |
dc.identifier.uri | http://hdl.handle.net/10234/89629 | |
dc.description.abstract | Water-soluble [M3S4X3(dhbupe)3]+ diphosphino complexes (dhbupe = 1,2-bis(bis(hydroxybutyl)phosphino)ethane), 1+ (M = Mo, X = Cl) and 2+ (M = W; X = Br), have been synthesized by extending the procedure used for the preparation of their hydroxypropyl analogues by reaction of the M3S4(PPh3)3X4(solvent)x molecular clusters with the corresponding 1,2-bis- (bishydroxyalkyl)diphosphine. The solid state structure of the [M3S4X3(dhbupe)3]+ cation possesses a C3 symmetry with a cuboidal M3S4 unit, and the outer positions are occupied by one halogen and two phosphorus atoms of the diphosphine ligand. At a basic pH, the halide ligands are substituted by hydroxo groups to afford the corresponding [Mo3S4(OH)3(dhbupe)3]+ (1OH+ ) and [W3S4(OH)3(dhbupe)3] + (2OH+ ) complexes. This behavior is similar to that found in 1,2-bis(bis(hydroxymethyl)phosphino)ethane (dhmpe) complexes and differs from that observed for 1,2-bis(bis(hydroxypropyl)phosphino)ethane (dhprpe) derivatives. In the latter case, an alkylhydroxo group of the functionalized diphosphine replaces the chlorine ligands to afford Mo3S4 complexes in which the deprotonated dhprpe acts in a tridentate fashion. Detailed studies based on stopped-flow, 31P{1 H} NMR, and electrospray ionization mass spectrometry techniques have been carried out in order to understand the solution behavior and kinetics of interconversion between the different species formed in solution: 1 and 1OH+ or 2 and 2OH+ . On the basis of the kinetic results, a mechanism with two parallel reaction pathways involving water and OH− attacks is proposed for the formal substitution of halides by hydroxo ligands. On the other hand, reaction of the hydroxo clusters with HX acids occurs with protonation of the OH− ligands followed by substitution of coordinated water by X−. | ca_CA |
dc.format.extent | 10 p. | ca_CA |
dc.format.mimetype | application/pdf | ca_CA |
dc.language.iso | eng | ca_CA |
dc.publisher | American Chemical Society | ca_CA |
dc.relation.isPartOf | Inorganic Chemistry, 2013, vol. 52, no 15 | ca_CA |
dc.rights.uri | http://rightsstatements.org/vocab/CNE/1.0/ | * |
dc.subject | Clusters Bearing Hydroxyalkyl Diphosphines | ca_CA |
dc.subject | Kinetics of Substitution Reactions of Water-Soluble M3S4 (M = Mo, W) | ca_CA |
dc.title | Influence of the Ligand Alkyl Chain Length on the Solubility, Aqueous Speciation, and Kinetics of Substitution Reactions of Water-Soluble M3S4 (M = Mo, W) Clusters Bearing Hydroxyalkyl Diphosphines | ca_CA |
dc.type | info:eu-repo/semantics/article | ca_CA |
dc.identifier.doi | http://dx.doi.org/10.1021/ic400897y | |
dc.rights.accessRights | info:eu-repo/semantics/restrictedAccess | ca_CA |
dc.relation.publisherVersion | http://pubs.acs.org/doi/abs/10.1021/ic400897y | ca_CA |
dc.type.version | info:eu-repo/semantics/publishedVersion | ca_CA |
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